1-alkyl-4-oxophosphorinanium halides



United States Patent 3,316,304 1-ALKYL-4-0XOPHOSPHORINANIUM HALIDES Richard Parke Welcher, Old Greenwich, Conn., assignor to American Cyanamid Company, Stamford, Conn., a Corporation of Maine No Drawing. Original application Dec. 22, 1961, Ser. No. 161,438, now Patent No. 3,225,103, dated Dec. 21, 1965. Divided and this application Aug. 9, 1965, Ser.

ticularly, the instant discovery relates to 4-phosphorinanone derivatives of the formulae:

ill

IIVOH R in the above formulae represents a member selected from the group consisting of substituted and unsubstituted, branched and straight chain alkyl (C -C substituted and unsubstituted cycloalkyl, substituted and unsubstituted aryl; R R R and R each represent a member selected from the group consisting of hydrogen, lower alkyl, phenyl, chloro-substituted phenyl, lower alkyl-substituted phenyl, cyclohexyl and lower alkoxyalkyl; R and R each represent a member selected. from the group consisting of hydrogen, lower alkyl and phenyl; and R represents alkyl having from 1 to 12 carbon atoms.

The 4-phosphorinanone reactants are prepared according to copending US. application, Ser. No. 161,405, filed Dec. 22, 1961, and now abandoned, by reacting a primary phosphine RPH with a divinyl ketone (1,4-dien-3-one) of the formula and recovering the corresponding phosphorinanone.

The primary phosphine reactant and the 1,4-dien-3one reactant are best reacted at a temperature in the range of C. to 200 C. and recovering the resulting 4-phosphorinanone product by volatilization, for example, at a reduced pressure in the range of 0 to 760 millimeters. Reaction is best carried out in a substantially inert atmosphere, such as in a nitrogen or helium atmosphere, or the like. No catalyst or solvent is necessary for the process contemplated herein.

Furthermore, the process is generally carried out at atmospheric pressure. Superatmosphen'c pressures as high as 700 pounds per square inch may likewise be used, particularly with low boiling reactants. Usually, however, very good results are achieved at atmospheric pressure.

Similarly, stoichiometric generally employed.

quantities of the reactants are Nevertheless, small excesses of either reactant may be present without detrimentally affecting the nature of the reaction.

Generally, the reactants are heated for at least one hour, but this is not critical since incipient reaction occurs upon intermingling the reactants.

Typical primary phosphines useful for producing phosphorinanone reactants within the purview of the instant discovery are phenylphosphine, cyclohexylphosphine, dodecylphosphine, isopropylphosphine, benzylphosphine, 2- ethoxyethylphosphine, Z-cyanoethylphosphine, para-chlorophenylphosphine, methylphosphine, .isobutylphosphine, ethylphosphine propylphosphine, butylphosphine, pentylphosphine, hexylphosphine, octylphosphine, heptylphos phine, decylphosphine, undecylphosphine, heptadecylphosphine, octadecylphosphine, etc.

It follows from the above listing that typical substituents for primary alkyl phosphine are lower alkoXy, phenyl, cyano and the like. Typical substituents for primary aryl phosphine, such as phenyl phosphine, are halogen (e.g. Cl, Br, and I) lower alkyl, etc.

In other words, substituents which do not interfere with, enter into, i.e., are inert under the conditions of, the reaction for preparing 4-phosphorinanones are contemplated herein.

The 4-phosphorinanone reactants prepared as above may be converted to the products of the present invention according to the following typical and conventional processes:

1-phenyl-4-phosphorinanone and zinc, respectively.

para-nitrophenylhydra EXAMPLE 6 2,2,6-trimethyZ-1-plzenyI-4-ph0sphorinanone, oxime 5 EXAMPLE 1 One part hydroxylamine hydrochloride is dissolved i1 6 parts of H 0. To this is added 4 parts of NaOE 2,2,6,6-termmcthyl-1-phenyl-4-phosph0rinrm0ne-l-sulfide solution and 0.4 part 2,2,6-trimethyl- 1 phenyl-4-phosphorinanone. The resulting mixture is warmed for 1( A nz n s u i n of 1- g s of r m t y1- 10 minutes on a steam bath, cooled and the resulting 2,2,6- 1-phenyl-4-phosphorinanone and 0.28 gram of sulfur is trimethyl-l-phenyl-4-ph0sph0rinan0ne oxime product heated at 80 C. for '30 minutes. Recrystallization of crystals filtered off. the product from methanol and hexane yields 2,2,6,6- Examples 1, 2, 3, 4, 5 and 6 are repeated in every tetramethyl-l-phenyl-4-phosphorinanone-1-sulfide melting essential respect substituting the respective 4-phosphorat 138 C. 139 C. inanone reactants as indicated in the following table.

TABLE II Ex. Tempcra- Reaction N o. Reactant-4-Phosphormanone Other Reactant ture, 0. According Product to Example 7 l-cyclohexyl-2-cthyl-4-phosphorirlanone. Excess heptyl bromide 50 2 l-cyclohexyl-l heptyI-Q-ethyM-phosphorinanium bromide. 8 1-dodecyl-2,2-dipropyl-4-phosphor- Excess benzyl chloride 80 2 l-benzyl-l-rlcdecyl-2,Z-dipmpyH-phosinanone. phorinanium chloride. 9 2butyl-2(Z-methoXy-ethy1)-1-0cl;yl-4- Dodecylrodlde 2 2-butyl-1-dodecyl-2-(2-methoxy-cthyl)-1- phosphorinanone. octyl-4-phosphorinauium iodide. 10 2,2,6,6-tetraethy1-3,5 dimethy1-Lpheny1- Propylbromlde 24 2 2,2,6,6tctraethyl-,fi-dirnethyl-propyl-l- 4-phosphorinanone. phenyll-phosphorinanium chloride. 11 l-pr0py1-2,6-diisopr0py1phenyl-4-ph0s- Sulfur 50 1 1-propyl-2.G-di-isopropylphenyM-phosphorinanone. phorinanone--1-sulfide. 12 1-(2-ethoxyethyl)-2,2,6,6-tetraethyl-4- .d0 110 1 1-(2-ethoxyethyl)-2,2,6,6-tetraethyl-4- phosphorinenone. phosphorinanone-l-sulfide. 13 2,2-diethyl-1-octadecy1-4-phosph0r- Phenylhydrazlue 60 4 2,2-diethyl-Loctadceyl--phosphorinanone. inanone, phenylhydrazone. 14 24sobutyl-1-methyl-4-phosphor1nanone Para-nltro-phenylhydrazine.- 78 5 2-isobutyl-Lmethyl-4-phosphorinanone A para-nitro-phenylhydrazone. 15. l-phenyl-3,fi-dipropylt phosphor- Semrcarbazrde HCl and au- 90 3 1-phenyl-3.5-dipropyl-4-phosphorinaninanone. htydrous potassium earbonone, semicarbazone.

a e. 16 2-methyl-1,2-dipheuyl-4-phosphorin- Hydroxylamine hydrochlo- 90 6 2-methyl-1,2-dipheuyl-4-phosphorinanone. ride and base. anone, oxime.

EXAMPLE 2 1 -ethyl-1 -methyl-4-0x0phosph0rinanium iodide A mixture of 0.4 gram of l-ethyl-4-phosphorinanone and 4 grams of methyl iodide in 20 milliliters of ether under a nitrogen atmosphere gives a white precipitate on standing. The compound 1-ethyl-1-methyl-4-oxophosphorinanium iodide results. After recrystallization from acetone (1 gram/130 milliliters) its melting point is 213 C.-214 C.

EXAMPLE 3 1,2,6-triphenyl-4-ph0sphorinanone, .remicarbazone EXAMPLE 4 1-heptadecyl-2,2,6,6-tetramethyl-4-ph0sphorinanone, phenylhydrazone One part of 1-heptadecyl-2,2,6,6-tetramethyl-4-phosporinanone, one part phenylhydrazine and 20 parts of ethanol are mixed and heated to boiling under nitrogen. A drop of glacial acetic acid is added after several minutes. Water is then added until solution is cloudy, then the solution is cooled and filtered thus recovering the product l-heptadecyl 2,2,6,6 tetramethyl 4 phosphorinanone,

phenylhydrazone.

EXAMPLE 5 Z-methyl-1-phenyl-4-phosphorinan0ne, para-nitrophenylhydrazone Example 4 is repeated in every essential respect substituting the ketone and hydrazine reactant with Z-methyl- The sulfide derivatives of the present invention are best produced by reacting stoichiometric amounts of sulfur and the 4-phosphorinanone reactant at temperatures in the range of 50 C. to 150 C. and in the presence of an inert organic solvent. Usually the reaction is carried out at a temperature below the boiling point of the solvent. Typical solvents are aromatic hydrocarbons, e.g., benzene, toluene, xylene, and the like. The resulting product is recovered by recrystallization. The 4-oxophosphorinanium halides are generally produced by reacting stoichiometric amounts of an alkyl halide and a 4-phosphorinanone in a nitrogen atmosphere and in the presence of an ether solvent, or excess alkyl halide, at a temperature in the range of 0 C. to C., preferably temperatures below the boiling point of the ether solvent when used.

The semicarbazone derivatives of the present invention are usually carried out by reacting semicarbazide hydrochloride with a weak inorganic or organic base, such as potassium carbonate, sodium acetate, and the like, in the presence of a lower alkanol and at a temperature in the range of 40 C. to C.

As to the phenylhydrazone derivatives of the instant discovery, the production thereof is generally accomplished by reacting a phenylhydrazine with a 4-phosphorinanone under nitrogen and in the presence of a lower alkanol. Temperatures in the range of 50 C. to 100 C. are generally employed.

The para-nitro-phenylhydrazone derivatives are produced in the same manner as the phenylhydrazone derivatives, save that para-nitro-phenylhydrazone is used in lieu of phenylhydrazine.

The oxime derivatives of the present invention are prepared as in Example 4, above, using hydroxylamine hydrochloride, and an equivalent amount, basis the hydroxylamine hydrochloride, of alkali metal hydroxide. The solvent used is water and temperatures in the range of 50 C. to 100 C. are employed.

The 4-phosphorinanone derivatives of the present inven- )11 have direct utility as gasoline additives. For example,

a to about 10 milliliters of any one of these derivatives,

hen dissolved in one gallon of gasoline, affords protec- Jn against misfiring, surface ignition, a

Clearly, the instant .odifications within the skill of the art.

nd the like.

discovery encompasses numerous Consequently,

hile the present invention has been described in detail ith respect to specific embodiments thereof, it is not ltended that these details be construed as limitations upon 1e scope of the invention, except insof 1 the appended claims.

ar as they appear I claim: 1. A 1-alky1-4-oxophosphorinanium halide of the foriula 0 ll C R -CH HCRB IL -C JR R /0\ R e; R Xe )f substituted and unsubstituted, bran ched and straight 8 chain alkyl having from 1 to 18 carbon atoms, cyclohexyl, phenyl, and substituted phenyl; said substituents for alkyl being selected from the group consisting of lower alkoxy, phenyl and cyano, and said substituents for phenyl being selected from the group consisting of halogen and lower alkyl; R R R and R each represent a member selected from the group consisting of hydrogen, lower alkyl, phenyl, chloro-substituted phenyl, lower alkyl-substituted phenyl, cyclohexyl and lower alkoxy-alkyl; and R and R each represent a member selected from the group consisting of hydrogen, lower alkyl and phenyl; X is a member selected from the group consisting of Br, Cl and l; and R" represents alkyl having'from 1 to 12 carbon atoms.

2. l-ethyl-1-methyl-4-oxophosphorinanium iodide.

OTHER REFERENCES Welcher et al., J. Org. Chem. 27, 1824-1827 (1962).

LEON ZITVER, Primary Examiner.

25 DANIEL D. HORWITZ, Examiner. 

1. A 1-ALKYL-4-OXOPHOSPHORINANIUM HALIDE OF THE FORMULA 